METALLOCENE POLYMERS .35. POLYFERROCENYLENES BY OXIDATIVE COUPLING OF 1,1'-DILITHIOFERROCENE WITH CU2+ ION

The oxidative coupling of 1,1 ′-dilithioferrocene (chelated with N,N,N′,N′-tetramethylethylenediamine) in the presence of CuII halide (Cu2+:Li=1-1.5) in ether solvents at -70 to 110° gives 30-45% yields of polyferrocenylene. Still higher yields of coupling products result from reactions in which oxidative coupling is paired with thermal coupling, i. e. C-C bond formation through thermal decomposition of organocopper(I) intermediates in the absence of external oxidant (Cu2+:Li=0.5). Number-average molecular masses of the highest fractions of linear products (2) as separated in the primary work-up process are in the 1500-3400 range, and fractionating precipitation results in subfractions with Mn as high as 5000. Cyclization of dinuclear intermediates, producting up to 10% of [0,0] ferrocenophane (bisfulvalenediiron), competes in all experiments with linear propagation. Experiments conducted with CuI halides under conditions leading exclusively to thermal coupling provide even higher conversion to the ferrocenophane (up to 25% yields) at the expense of linear condensation products. Spectroscopic features of the polyferrocenylenes are discussed. In the linear compounds with -Mn>800, i.r. absorptions and p.m.r.'s are remarkably invariant with the degree of polymerization, as are the electronic absorption maxima. This shows, in confirmation of earlier reports, that there is insignificant resonance interaction between the cyclopentadienyl rings in the ferrocene system and hence little, if any, electronic delocalization along the polymer chain of heteroannularly interlinked polyferrocenylene structures. © 1979 Verlag Chemie, Gmbh.